CN114011342A - System and method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide - Google Patents
System and method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide Download PDFInfo
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Abstract
The invention relates to a system for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide, which comprises a dehydration reactor, a cycloaddition reactor, an epoxy compound raw material storage tank, a carbonate product storage tank and an ethylene glycol or 1, 2-propylene glycol product storage tank. The inlet of the dehydration reactor is connected with an industrial tail gas carbon dioxide input pipe, and the outlet is connected with a booster fan through a deep desulfurization/denitrification device and a buffer air bag; the cycloaddition reactor is connected with a carbonate product storage tank, the top of the cycloaddition reactor is provided with a discharge pipe, and the middle of the cycloaddition reactor is provided with an alkaline catalyst input port; the upper part in the cycloaddition reactor is provided with a sprayer which is connected with an epoxy compound raw material storage tank; a carbon dioxide gas distributor connected with a booster fan is arranged at the bottom in the cycloaddition reactor; the collecting device of the dehydration reactor is connected with the output pipe of the filling pump, and the bottom of the dehydration reactor is connected with the ethylene glycol or 1, 2-propylene glycol product storage tank. Meanwhile, the invention also discloses a method for preparing the cyclic carbonate by converting the industrial tail gas into carbon dioxide. The invention can save investment and operation cost.
Description
Technical Field
The invention relates to the technical field of carbon neutralization, in particular to a system and a method for preparing cyclic carbonate by converting industrial tail gas carbon dioxide.
Background
Since the first industrial revolution started in the 60 s of the 18 th century, the human beings greatly improve the social productivity and promote the economic development and social progress by using fossil energy such as coal, petroleum, natural energy and the like; however, with the use of fossil energy, carbon elements buried underground in the form of coal, oil, natural gas, etc. are discharged into the atmosphere in the form of gaseous carbon dioxide, so that the global atmospheric carbon dioxide concentration is suddenly increased from 260ppm before the industrial revolution to 419ppm (2021, 5 months), and thus, climate change, natural disaster frequency, ecosystem disturbance are brought, and great harm is brought to human lives and properties and living environment.
By 22 months 4 in 2021, more than 120 countries around the world announce the goal of carbon neutralization! In order to achieve the goals of carbon peak reaching and carbon neutralization, the scale conversion and utilization of carbon dioxide is one of effective routes for carbon fixation. However, the traditional CCS or CCUS must first perform carbon capture, and the process has the disadvantages of large investment, high operation energy consumption, large degradation loss of the absorbent, strong corrosion of equipment and the like, thus hindering the popularization of the technology.
CO2As a cheap, abundant and easily available carbon resource, the method can be converted into a chemical with high economic value under mild conditions, and has important ring for relieving greenhouse effect, improving energy utilization rate and the likeEnvironmental benefit and economic value. In view of the current environmental problems and the demand for chemicals, CO2Has become a focus of global attention.
Common CO2The trapping and separating technology is the absorption of amine solution, has high efficiency and trapping amount, but has the problems of serious corrosion of equipment, high regeneration energy consumption and the like. Furthermore, it is generally necessary to subject the captured CO to2The gas is compressed and sealed, so that the desorption and compression energy consumption is high, the gas can be leaked, and the operation cost is high. CO 22The cycloaddition reaction being CO2One of the important ways of conversion and utilization is that the reaction has 100% atom economy, and the generated cyclic carbonate is a chemical product with high value and wide application. At present, alkali metal salts, metal halides, ionic liquids and the like have been used as CO2The catalyst for cycloaddition reaction has the disadvantages of more or less complex catalyst synthesis method, low catalytic stability and reactivity, use of cosolvent, harsh reaction conditions and the like, and generally requires pure CO2Gas, high investment cost.
Therefore, there is a need to develop a material with low cost, environmental friendliness, easy regeneration and high catalytic activity to realize CO in flue gas2Direct catalytic conversion and reduction of CO in the environment2The emission amount, the equipment investment and the operation cost are reduced, and CO is realized2High efficiency utilization of the catalyst and long-term stability of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problem of providing a system for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide, which saves investment and operation cost.
The invention aims to solve another technical problem of providing a method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide.
In order to solve the above problems, the present invention provides a system for preparing cyclic carbonate by converting carbon dioxide, which is an industrial tail gas, comprising: the system comprises a dehydration reactor, a cycloaddition reactor, an epoxy compound raw material storage tank, a carbonate product storage tank and an ethylene glycol or 1, 2-propylene glycol product storage tank; the inlet of the dehydration reactor is connected with an industrial tail gas carbon dioxide input pipe through a flue gas induced draft fan, and the outlet of the dehydration reactor is connected with a booster fan through a deep desulfurization/denitrification device and a buffer air bag in sequence; the bottom of the cycloaddition reactor is connected with the carbonate product storage tank through a collection pump, the top of the cycloaddition reactor is provided with a discharge pipe connected with a tail gas treatment device, and the middle of the cycloaddition reactor is provided with an alkaline catalyst input port; a sprayer is arranged at the upper part in the cycloaddition reactor and is connected with the bottom of the epoxy compound raw material storage tank through a filling pump; a carbon dioxide gas distributor is arranged at the bottom in the cyclic addition reactor and is connected with an outlet of the booster fan; the collecting device of the dehydration reactor is connected with the output pipe of the filling pump, the bottom of the dehydration reactor is connected with the ethylene glycol or 1, 2-propylene glycol product storage tank through a collecting pump by a pipeline, and a solid base catalyst input pipeline is arranged.
3-5 reaction chambers are arranged in the dehydration reactor.
A method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide comprises the following steps:
the method comprises the steps that industrial tail gas containing moisture with the volume concentration of 5-10% enters a dehydration reactor through a flue gas induced draft fan, and flue gas and water with moisture removed are obtained respectively;
secondly, the flue gas of desorption moisture gets into degree of depth desulfurization/denitrification facility, obtains CO after getting rid of interfering substance2The volume concentration of the treated flue gas is 10-100%;
thirdly, adding an alkaline catalyst in the middle of the annular addition reactor, and simultaneously adding a solid alkaline catalyst at the bottom of the dehydration reactor;
the epoxy compound is sprayed at a constant speed of 200-1000 kg/h from the top of the cycloaddition reactor through a filling pump from an epoxy compound raw material storage tank, and the treated flue gas is sprayed at a speed of 1 x 10 through a buffering air bag and a booster fan3-2×103 m3Introducing the gas from the bottom of the cycloaddition reactor at a flow rate of/h, and performing cycloaddition reaction at 50-150 ℃ to respectively obtain tail gas A and cyclic carbonate; the cyclic carbonate enters a carbonate product storage tank through a collection pump;
simultaneously, epoxy compounds enter from the bottom of a dehydration reactor through a filling pump at a speed of 90-360 kg/h and react with the water obtained in the step to respectively obtain tail gas B and ethylene glycol or 1, 2-propylene glycol, and the ethylene glycol or the 1, 2-propylene glycol enters an ethylene glycol or 1, 2-propylene glycol product storage tank through a collection pump;
after the tail gas A and the tail gas B are collected, condensing and adsorbing treatment are carried out, unreacted raw materials and products brought out by the airflow are collected, and further treatment and recycling are carried out until the emission reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
The alkaline catalyst in the step three is a solid-phase ionic compound catalyst or a homogeneous molecular catalyst.
The solid-phase ionic compound catalyst is alkaline supported ionic liquid or alkaline polymerized ionic liquid.
The alkaline load ionic liquid is prepared by the following method: dispersing 1 part by mass of alkaline ionic liquid into 1-4 parts by mass of solvent to prepare alkaline ionic liquid solution, then adding 0.5-4 parts by mass of carrier, carrying out ultrasonic immersion treatment at room temperature-80 ℃ for 1-4 h at the power of 200W-800W, centrifuging or filtering for separation, washing for multiple times, and carrying out vacuum drying at 60-100 ℃ to obtain the alkaline ionic liquid;
the alkaline ionic liquid is one of imidazole, quaternary ammonium or quaternary phosphorus halides containing hydroxyl and imino, and the structural formula is as follows:
wherein: r and R' are the same or different and are alkyl with 1-12 carbon atoms; r' is hydrogen or C1-4 alkane; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I;
the carrier is one of silica gel, mesoporous alumina, molecular sieve, styrene resin, graphene, metal organic frameworks and derivatives thereof; the solvent is one of methanol, ethanol, acetonitrile, isopropanol, n-propanol, acetone or n-butanol.
The alkaline ionic liquid is prepared by the following method: firstly, preparing imidazole, alkylamine or alkylphosphoalkane containing halogen side chains by a conventional solvothermal method at 60-110 ℃ for 12-36 h; then reacting with halogen alkyl alcohol with the molar ratio of 1-1.2 at 40-80 ℃ for 6-24 h, and performing rotary evaporation, washing and drying at 60-80 ℃ to obtain imidazolium salt, quaternary ammonium salt or quaternary phosphonium salt with halogen side chains and hydroxyl side chains; the ionic salt and amino-containing molecules such as guanidine salt react for 12-24 hours at room temperature-80 ℃, and then the expected alkaline ionic liquid is obtained through rotary evaporation, washing and drying at 40-80 ℃.
The basic polymeric ionic liquid is an imidazole halide polymeric material containing hydroxyl, imino and styrene, and the structural formula of the basic polymeric ionic liquid is as follows:
wherein: x > 10; r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I;
the alkaline polymerization ionic liquid is prepared by the following method: the preparation method comprises the steps of taking azobisisobutyronitrile or di-tert-butyl peroxide as an initiator, dissolving a basic ionic liquid monomer containing vinyl in a solvent, reacting at 80-140 ℃ for 12-36 h, washing and drying to obtain the product.
The homogeneous molecular catalyst is one of alkaline ionic liquid 1- (4-formate) benzyl-3-alkyl imidazole halide, 1- (4-sulfonate) benzyl-3-alkyl imidazole halide and derivatives thereof, and the structural formula of the homogeneous molecular catalyst is as follows:
wherein: r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R' is a hydrogen atom or an alkane having 1 to 4 carbon atoms, M+Is metal ion Na+Or K+，M2+Is metal ion Mg2+And Zn2+，X=Cl、Br、I。
And step three, the solid base catalyst in the step three is one or more of zirconium oxide, calcium oxide and sodium carbonate.
Compared with the prior art, the invention has the following advantages:
1. the invention directly leads the industrial tail gas into the cycloaddition reactor for addition reaction after being treated by the dehydration reactor and the deep desulfurization/denitrification device without trapping and purifying carbon dioxide in the industrial tail gas in advance, thereby not only saving the investment and the operation cost of an industrial tail gas carbon trapping system, but also directly leading the industrial tail gas (treated N)2Concentration > 78%) as shielding gas, i.e. without additional consideration of the shielding gas N2The supply of (2).
2. The carbon dioxide conversion solid-phase catalyst can adapt to the reaction of carbon dioxide with the volume concentration of 10-100% and epoxy compounds, and can be operated for a long time without an additional regeneration step.
3. In the flue gas pretreatment link, the invention uses the chemical reaction principle for dehydration, namely, under the action of a catalyst, ethylene oxide (propylene oxide) reacts with the obtained water to generate an additional product ethylene glycol (or 1, 2-propylene glycol), thereby realizing the collection and reutilization of water in the flue gas, changing waste into valuable and saving industrial water consumption.
4. The equipment related to the process technology of the invention is a skid-mounted module (equipment in a dotted frame in the figure) which is formed by intensively mounting raw material (flue gas and epoxy compound) storage tanks and product (cyclic carbonate, ethylene glycol or 1, 2-propylene glycol) storage tanks, can flexibly expand the capacity and be moved, and is suitable for various CO2Concentration, smoke amount, product amount and the like.
5. The invention adopts a modularized carbon conversion scheme, is convenient for enterprises to gradually expand the scale of carbon neutralization through system integration, does not waste the investment in the early stage, can solve the worldwide problems of high construction investment and operation cost, high desorption and compression purification energy consumption, easy degradation of an absorbent, atmosphere pollution caused by degradation products, easy corrosion equipment of the absorbent and the like of the traditional industrial tail gas carbon dioxide trapping device, and can be applied to the direct conversion of carbon dioxide in the industries of coal and electricity, cement, steel, chemical industry, coking and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic structural diagram of the present invention.
In the figure: the method comprises the following steps of 1-a dehydration reactor, 2-a deep desulfurization/denitrification device, 3-a cycloaddition reactor, 4-an epoxy compound raw material storage tank, 5-a carbonic ester product storage tank, 6-ethylene glycol or 1, 2-propylene glycol product storage tank, 7-a flue gas induced draft fan, 8-a buffer air bag, 9-a booster fan, 10-a collecting pump, 11-a filling pump and 12-a collecting pump.
Detailed Description
As shown in fig. 1, a system for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide comprises a dehydration reactor 1, a cycloaddition reactor 3, an epoxy compound raw material storage tank 4, a carbonate product storage tank 5 and an ethylene glycol or 1, 2-propylene glycol product storage tank 6.
The inlet of the dehydration reactor 1 is connected with an industrial tail gas carbon dioxide input pipe through a flue gas induced draft fan 7, and the outlet of the dehydration reactor is connected with a booster fan 9 through a deep desulfurization/denitrification device 2 and a buffer air bag 8 in sequence; the bottom of the cycloaddition reactor 3 is connected with a carbonate product storage tank 5 through a collection pump 12, the top of the cycloaddition reactor is provided with a discharge pipe connected with a tail gas treatment device, and the middle part of the cycloaddition reactor is provided with an alkaline catalyst input port; the upper part in the cycloaddition reactor 3 is provided with a sprayer to ensure the uniform distribution of the epoxy compound raw material, and the sprayer is connected with the bottom of an epoxy compound raw material storage tank 4 through a filling pump 11; a carbon dioxide gas distributor is arranged at the bottom in the cycloaddition reactor 3 to ensure that the carbon dioxide raw material is uniformly distributed, and the carbon dioxide gas distributor is connected with an outlet of a booster fan 9; the collecting device of the dehydration reactor 1 is connected with the output pipe of the filling pump 11, the bottom of the dehydration reactor is connected with the ethylene glycol or 1, 2-propylene glycol product storage tank 6 through the collecting pump 10 by a pipeline, and the dehydration reactor is provided with a solid base catalyst input pipeline.
Wherein: 3-5 reaction chambers are arranged in the dehydration reactor 1, and water in the flue gas is completely removed through continuous multi-stage reaction.
The dehydration reactor 1, the deep desulfurization/denitration device 2, the cycloaddition reactor 3, the buffer airbag 8, the booster fan 9, the collection pump 10, the filling pump 11 and the collection pump 12 can form a skid-mounted module so as to facilitate assembly, expansion and migration.
A method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide comprises the following steps:
the industrial tail gas containing moisture with volume concentration of 5-10% enters a dehydration reactor 1 through a flue gas induced draft fan 7, and flue gas and water with moisture removed are obtained respectively.
The flue gas with the moisture removed enters a deep desulfurization/denitrification device 2, and CO is obtained after interfering substances are removed2The volume concentration of the treated flue gas is 10-100%.
Wherein: the deep desulfurization/denitrification adopts the mature process with strong adsorption capacity of activated carbon, molecular sieve or resin and the like in the current industrial production.
Thirdly, 0.2-2.0 kg of alkaline catalyst is added to the middle part of the cycloaddition reactor 3 to realize the expected reaction; and simultaneously adding 0.1-0.5 kg of solid base catalyst at the bottom of the dehydration reactor 1 for the reaction of the epoxy compound and the moisture.
The basic catalyst refers to a solid-phase ionic compound catalyst or a homogeneous molecular catalyst. When a solid-phase ionic compound catalyst is adopted, a reaction bed layer is arranged in the middle of the cycloaddition reactor 3; when a homogeneous molecular catalyst is used, the cycloaddition reactor 3 is of the batch kettle type.
The solid-phase ionic compound catalyst refers to alkaline supported ionic liquid or alkaline polymerized ionic liquid.
The basic ionic liquid can be embedded into the pore channels of the porous carrier by adopting a physical impregnation method under the heating or ultrasonic condition.
Therefore, the alkaline supported ionic liquid can be prepared by adopting the following method preferentially: dispersing 1 part by mass of alkaline ionic liquid into 1-4 parts by mass of solvent to prepare alkaline ionic liquid solution, then adding 0.5-4 parts by mass of carrier, carrying out ultrasonic immersion treatment at room temperature-80 ℃ for 1-4 h at the power of 200W-800W, carrying out centrifugal or filtration separation, washing for multiple times to obtain white or light yellow solid, and finally carrying out vacuum drying at 60-100 ℃ to obtain the product.
The basic ionic liquid is one of imidazole, quaternary ammonium or quaternary phosphorus halides containing hydroxyl and imino, and the structural formula is as follows:
wherein: r and R' are the same or different and are alkyl with 1-12 carbon atoms; r' is hydrogen or C1-4 alkane; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I.
The alkaline ionic liquid is prepared by the following method: firstly, preparing imidazole, alkylamine or alkylphosphoalkane containing halogen side chains by a conventional solvothermal method at 60-110 ℃ for 12-36 h; then reacting with halogen alkyl alcohol with the molar ratio of 1-1.2 at 40-80 ℃ for 6-24 h, and performing rotary evaporation, washing and drying at 60-80 ℃ to obtain imidazolium salt, quaternary ammonium salt or quaternary phosphonium salt with halogen side chains and hydroxyl side chains; the ionic salt and amino-containing molecules such as guanidine salt react for 12-24 hours at room temperature-80 ℃, and then the expected alkaline ionic liquid is obtained through rotary evaporation, washing and drying at 40-80 ℃.
The carrier is one of silica gel, mesoporous alumina, molecular sieve, styrene resin, graphene, metal organic framework and derivatives thereof; the solvent is one of methanol, ethanol, acetonitrile, isopropanol, n-propanol, acetone or n-butanol.
The basic polymeric ionic liquid is imidazole halide polymeric material containing hydroxyl, imino and styrene, and the structural formula of the basic polymeric ionic liquid is as follows:
wherein: x > 10; r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I;
the alkaline polymerization ionic liquid is prepared by the following method: the preparation method comprises the steps of taking azobisisobutyronitrile or di-tert-butyl peroxide as an initiator, dissolving a basic ionic liquid monomer containing vinyl in a solvent, reacting at 80-140 ℃ for 12-36 h, washing and drying to obtain the product.
The homogeneous molecular catalyst is one of alkaline ionic liquid 1- (4-formate) benzyl-3-alkyl imidazole halide, 1- (4-sulfonate) benzyl-3-alkyl imidazole halide and derivatives thereof, and the structural formula of the homogeneous molecular catalyst is as follows:
wherein: r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R' is a hydrogen atom or an alkane having 1 to 4 carbon atoms, M+Is metal ion Na+Or K+，M2+Is metal ion Mg2+And Zn2+，X=Cl、Br、I。
The solid base catalyst is one or more of zirconia, calcium oxide and sodium carbonate.
The epoxy compound is sprayed from an epoxy compound raw material storage tank 4 through a filling pump 11 from the top of the cycloaddition reactor 3 at a constant speed of 200-1000 kg/h, and the treated flue gas is sprayed at a speed of 1 x 10 through a buffering air bag 8 and a booster fan 93-2×103 m3Introducing the gas from the bottom of the cycloaddition reactor 3 at a flow rate of/h, and performing cycloaddition reaction at 50-150 ℃ to respectively obtain tail gas A and cyclic carbonate; the cyclic carbonate enters the carbonate product storage tank 5 via the collection pump 12.
Meanwhile, epoxy compounds enter from the bottom of the dehydration reactor 1 at a speed of 90-360 kg/h through the filling pump 11 and react with the water obtained in the step, so that tail gas B and ethylene glycol or 1, 2-propylene glycol are obtained respectively, and the ethylene glycol or 1, 2-propylene glycol enters the ethylene glycol or 1, 2-propylene glycol product storage tank 6 through the collection pump 10.
After the tail gas A and the tail gas B are converged, carrying out condensation and adsorption treatment, collecting unreacted raw materials and products brought out by the airflow, and carrying out further treatment and recycling until the exhaust reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
Embodiment 1 a method for preparing cyclic carbonate by carbon dioxide conversion of industrial tail gas, comprising the following steps:
the industrial tail gas containing moisture with the volume concentration of 5% enters a dehydration reactor 1 through a flue gas induced draft fan 7, and flue gas and water with moisture removed are obtained respectively.
Secondly, the flue gas of desorption moisture gets into degree of depth desulphurization denitration device 2, utilizes the active carbon wherein to get CO after getting rid of interfering substance2Treated flue gas with a concentration of 20% by volume.
Thirdly, 0.5 kg of 1- (guanidinomethyl) -3- (2-hydroxyethyl) imidazole bromine loaded styrene catalyst is added to the middle part of the cycloaddition reactor 3 for realizing the expected reaction; at the same time, 0.1 kg of solid base catalyst was added to the bottom of the dehydration reactor 1 for the reaction of the epoxy compound with moisture.
Wherein: the structural formula of the 1- (guanidinomethyl) -3- (2-hydroxyethyl) imidazole bromine catalyst is as follows:
the ethylene oxide is sprayed at a constant speed of 392 kg/h from the top of the cycloaddition reactor 3 through the injection pump 11 from the epoxy compound raw material storage tank 4, and the treated flue gas is sprayed at a constant speed of 1 × 10 through the buffer air bag 8 and the booster fan 93 m3Introducing the mixture from the bottom of the cycloaddition reactor 3 at a flow rate of/h, and respectively obtaining tail gas A and ethylene carbonate through a cycloaddition reaction at the temperature of 80 ℃; the ethylene carbonate enters the carbonate product tank 5 via a collection pump 12.
Meanwhile, ethylene oxide enters from the bottom of the dehydration reactor 1 at a rate of 98 kg/h through the filling pump 11 and reacts with the water obtained in the step, so that tail gas B and ethylene glycol are obtained respectively, and the ethylene glycol enters the ethylene glycol product storage tank 6 through the collecting pump 10.
After the tail gas A and the tail gas B are converged, carrying out condensation and adsorption treatment, collecting unreacted raw materials and products brought out by the airflow, and carrying out further treatment and recycling until the exhaust reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
Embodiment 2 a method for preparing cyclic carbonate by carbon dioxide conversion of industrial tail gas, comprising the following steps:
the industrial tail gas containing moisture with the volume concentration of 5% enters a dehydration reactor 1 through a flue gas induced draft fan 7, and flue gas and water with moisture removed are obtained respectively.
Secondly, the flue gas with the moisture removed enters a deep desulfurization/denitrification device 2, and the molecular sieve in the flue gas is utilized to remove interfering substances to obtain CO2Treated flue gas with a concentration of 15% by volume.
Thirdly, 0.8 kg of poly [ 1-p-styrene aminomethyl-3- (3-hydroxypropyl) imidazole chloride ] catalyst is added to the middle part of the cycloaddition reactor 3 to realize the expected reaction; at the same time, 0.1 kg of solid base catalyst was added to the bottom of the dehydration reactor 1 for the reaction of the epoxy compound with moisture.
Wherein: the structural formula of the poly [ 1-p-styrene aminomethyl-3- (3-hydroxypropyl) imidazole chloride ] catalyst is as follows:
the propylene oxide is sprayed from an epoxy compound raw material storage tank 4 through a filling pump 11 from the top of the cycloaddition reactor 3 at a constant speed of 588 kg/h, and the treated flue gas is sprayed at a speed of 2 x 10 through a buffer air bag 8 and a booster fan 93 m3The flow rate of the reaction solution is introduced from the bottom of the cycloaddition reactor 3, and the tail gas A and the propylene carbonate are respectively obtained through the cycloaddition reaction at the temperature of 100 ℃; the propylene carbonate enters the carbonate product tank 5 via the collection pump 12.
Simultaneously, propylene oxide enters from the bottom of the dehydration reactor 1 at a rate of 196 kg/h through the filling pump 11 and reacts with the water obtained in the step to respectively obtain tail gas B and 1, 2-propylene glycol, and the 1, 2-propylene glycol enters the 1, 2-propylene glycol product storage tank 6 through the collection pump 10.
After the tail gas A and the tail gas B are converged, carrying out condensation and adsorption treatment, collecting unreacted raw materials and products brought out by the airflow, and carrying out further treatment and recycling until the exhaust reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
Embodiment 3 a method for preparing cyclic carbonate by carbon dioxide conversion of industrial tail gas, comprising the following steps:
industrial tail gas containing water with the volume concentration of 10% enters a dehydration reactor 1 through a flue gas induced draft fan 7, and flue gas and water with water removed are obtained respectively.
The flue gas with the moisture removed enters a deep desulfurization/denitrification device 2, and the resin in the flue gas is utilized to remove interfering substances to obtain CO2Treated flue gas with a concentration of 30% by volume.
Thirdly, 1.5 kg of 1- (4-sodium formate) benzyl-3-butyl imidazole bromide catalyst is added to the middle part of the cycloaddition reactor 3 to realize the expected reaction; at the same time, 0.1 kg of solid base catalyst was added to the bottom of the dehydration reactor 1 for the reaction of the epoxy compound with moisture.
Wherein: the structural formula of the 1- (4-sodium formate) benzyl-3-butyl imidazole bromide catalyst is as follows:
the epoxy ethane is sprayed at a constant speed of 882 kg/h from the top of the cycloaddition reactor 3 through the epoxy compound raw material storage tank 4 via the filling pump 11, and the treated flue gas is sprayed at a constant speed of 1.5 multiplied by 10 through the buffering air bag 8 and the booster fan 93 m3The flow rate of the catalyst is introduced from the bottom of the cycloaddition reactor 3, and the tail gas A and the carbon are respectively obtained through the cycloaddition reaction at the temperature of 80 DEG CVinyl acetate ester; the ethylene carbonate enters the carbonate product tank 5 via a collection pump 12.
Meanwhile, ethylene oxide enters from the bottom of the dehydration reactor 1 at a rate of 294 kg/h through the filling pump 11 and reacts with the water obtained in the step, so that tail gas B and ethylene glycol are obtained respectively, and the ethylene glycol enters the ethylene glycol product storage tank 6 through the collecting pump 10.
After the tail gas A and the tail gas B are converged, carrying out condensation and adsorption treatment, collecting unreacted raw materials and products brought out by the airflow, and carrying out further treatment and recycling until the exhaust reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
Claims (10)
1. A system for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide is characterized in that: the system comprises a dehydration reactor (1), a cycloaddition reactor (3), an epoxy compound raw material storage tank (4), a carbonate product storage tank (5) and an ethylene glycol or 1, 2-propylene glycol product storage tank (6); the inlet of the dehydration reactor (1) is connected with an industrial tail gas carbon dioxide input pipe through a flue gas induced draft fan (7), and the outlet of the dehydration reactor is connected with a booster fan (9) through a deep desulfurization/denitrification device (2) and a buffer air bag (8) in sequence; the bottom of the cycloaddition reactor (3) is connected with the carbonate product storage tank (5) through a collection pump (12), the top of the cycloaddition reactor is provided with a discharge pipe connected with a tail gas treatment device, and the middle of the cycloaddition reactor is provided with an alkaline catalyst input port; a sprayer is arranged at the upper part in the cycloaddition reactor (3) and is connected with the bottom of the epoxy compound raw material storage tank (4) through a filling pump (11); a carbon dioxide gas distributor is arranged at the bottom in the cycloaddition reactor (3) and is connected with an outlet of the booster fan (9); the collecting device of the dehydration reactor (1) is connected with the output pipe of the filling pump (11), the bottom of the dehydration reactor is connected with the ethylene glycol or 1, 2-propylene glycol product storage tank (6) through a pipeline by a collecting pump (10), and a solid base catalyst input pipeline is arranged.
2. The system for preparing the cyclic carbonate by converting the carbon dioxide of the industrial tail gas as claimed in claim 1, wherein: 3-5 reaction chambers are arranged in the dehydration reactor (1).
3. A method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide comprises the following steps:
the method comprises the steps that industrial tail gas containing moisture with the volume concentration of 5-10% enters a dehydration reactor (1) through a flue gas induced draft fan (7), and flue gas and water with moisture removed are obtained respectively;
secondly, the flue gas with the moisture removed enters a deep desulfurization/denitrification device (2), and CO is obtained after interfering substances are removed2The volume concentration of the treated flue gas is 10-100%;
thirdly, adding an alkaline catalyst in the middle of the cycloaddition reactor (3), and adding a solid alkaline catalyst at the bottom of the dehydration reactor (1);
the epoxy compound is sprayed from an epoxy compound raw material storage tank (4) through a filling pump (11) from the top of the cycloaddition reactor (3) at a constant speed of 200-1000 kg/h, and the treated flue gas passes through a buffering air bag (8) and a booster fan (9) and is sprayed at a speed of 1 x 103-2×103 m3Introducing the gas from the bottom of the cycloaddition reactor (3) at a flow rate of/h, and performing cycloaddition reaction at 50-150 ℃ to respectively obtain tail gas A and cyclic carbonate; the cyclic carbonate enters a carbonate product storage tank (5) through a collection pump (12);
simultaneously, epoxy compounds enter from the bottom of the dehydration reactor (1) through a filling pump (11) at a speed of 90-360 kg/h and react with the water obtained in the step to respectively obtain tail gas B and ethylene glycol or 1, 2-propylene glycol, and the ethylene glycol or the 1, 2-propylene glycol enters an ethylene glycol or 1, 2-propylene glycol product storage tank (6) through a collecting pump (10);
after the tail gas A and the tail gas B are collected, condensing and adsorbing treatment are carried out, unreacted raw materials and products brought out by the airflow are collected, and further treatment and recycling are carried out until the emission reaches the standard; while the basic catalyst in the cycloaddition reaction, the solid basic catalyst in the hydration reaction are regenerated by filtering, centrifuging or removing the product by distillation and used for the next cycle.
4. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 3, which is characterized in that: the alkaline catalyst in the step three is a solid-phase ionic compound catalyst or a homogeneous molecular catalyst.
5. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 4, characterized by comprising the following steps: the solid-phase ionic compound catalyst is alkaline supported ionic liquid or alkaline polymerized ionic liquid.
6. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 5, which is characterized in that: the alkaline load ionic liquid is prepared by the following method: dispersing 1 part by mass of alkaline ionic liquid into 1-4 parts by mass of solvent to prepare alkaline ionic liquid solution, then adding 0.5-4 parts by mass of carrier, carrying out ultrasonic immersion treatment at room temperature-80 ℃ for 1-4 h at the power of 200W-800W, centrifuging or filtering for separation, washing for multiple times, and carrying out vacuum drying at 60-100 ℃ to obtain the alkaline ionic liquid;
the alkaline ionic liquid is one of imidazole, quaternary ammonium or quaternary phosphorus halides containing hydroxyl and imino, and the structural formula is as follows:
wherein: r and R' are the same or different and are alkyl with 1-12 carbon atoms; r' is hydrogen or C1-4 alkane; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I;
the carrier is one of silica gel, mesoporous alumina, molecular sieve, styrene resin, graphene, metal organic frameworks and derivatives thereof; the solvent is one of methanol, ethanol, acetonitrile, isopropanol, n-propanol, acetone or n-butanol.
7. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 6, which is characterized in that: the alkaline ionic liquid is prepared by the following method: firstly, preparing imidazole, alkylamine or alkylphosphoalkane containing halogen side chains by a conventional solvothermal method at 60-110 ℃ for 12-36 h; then reacting with halogen alkyl alcohol with the molar ratio of 1-1.2 at 40-80 ℃ for 6-24 h, and performing rotary evaporation, washing and drying at 60-80 ℃ to obtain imidazolium salt, quaternary ammonium salt or quaternary phosphonium salt with halogen side chains and hydroxyl side chains; the ionic salt and amino-containing molecules such as guanidine salt react for 12-24 hours at room temperature-80 ℃, and then the expected alkaline ionic liquid is obtained through rotary evaporation, washing and drying at 40-80 ℃.
8. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 5, which is characterized in that: the basic polymeric ionic liquid is an imidazole halide polymeric material containing hydroxyl, imino and styrene, and the structural formula of the basic polymeric ionic liquid is as follows:
wherein: x > 10; r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; m and n are the same or different and have a value of 1 to 4; x = Cl, Br, I;
the alkaline polymerization ionic liquid is prepared by the following method: the preparation method comprises the steps of taking azobisisobutyronitrile or di-tert-butyl peroxide as an initiator, dissolving a basic ionic liquid monomer containing vinyl in a solvent, reacting at 80-140 ℃ for 12-36 h, washing and drying to obtain the product.
9. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 4, characterized by comprising the following steps: the homogeneous molecular catalyst is one of alkaline ionic liquid 1- (4-formate) benzyl-3-alkyl imidazole halide, 1- (4-sulfonate) benzyl-3-alkyl imidazole halide and derivatives thereof, and the structural formula of the homogeneous molecular catalyst is as follows:
wherein: r is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R' is a hydrogen atom or an alkane having 1 to 4 carbon atoms, M+Is metal ion Na+Or K+，M2+Is metal ion Mg2+And Zn2+，X=Cl、Br、I。
10. The method for preparing cyclic carbonate by converting industrial tail gas into carbon dioxide according to claim 3, which is characterized in that: and step three, the solid base catalyst in the step three is one or more of zirconium oxide, calcium oxide and sodium carbonate.
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